Growth of very uniform silicon carbide epitaxial layers

ABSTRACT

An improved chemical vapor deposition method is disclosed that increases the uniformity of silicon carbide epitaxial layers and that is particularly useful for obtaining thicker epitaxial layers. The method comprises heating a reactor to a temperature at which silicon carbide source gases will form an epitaxial layer of silicon carbide on a substrate in the reactor; and then directing a flow of source and carrier gases through the heated reactor to form an epitaxial layer of silicon carbide on the substrate with the carrier gases comprising a blend of hydrogen and a second gas in which the second gas has a thermal conductivity that is less than the thermal conductivity of hydrogen so that the source gases deplete less as they pass through the reactor than they would if hydrogen is used as the sole carrier gas.

FIELD OF THE INVENTION

The present invention relates to the epitaxial growth of siliconcarbide, and in particular relates to a method of chemical vapordeposition that produces very uniform epitaxial layers of siliconcarbide on appropriate substrates.

BACKGROUND OF THE INVENTION

The present invention relates to the growth of silicon carbide epitaxiallayers. As a semiconductor material, silicon carbide is particularlysuperior for high power, high frequency, and high temperature electronicdevices. Silicon carbide has an extremely high thermal conductivity, andcan withstand both high electric fields and high current densitiesbefore breakdown. Silicon carbide's wide band gap results in low leakagecurrents even at high temperatures. For these and other reasons, siliconcarbide is a quite desirable semiconductor material for power devices;i.e., those designed to operate at relatively high voltages.

Silicon carbide is, however, a difficult material to work with. Growthprocesses must be carried out at relatively high temperatures, above atleast about 1500° C. for epitaxial growth and approximately 2200° C. forsublimation growth. Additionally, silicon carbide can form over 150polytypes, many of which are separated by small thermodynamicdifferences. As a result, single crystal growth of silicon carbide,either by epitaxial layer or bulk crystal, is a challenging process.Finally, silicon carbide's extreme hardness (it is most oftenindustrially used as an abrasive material) contributes to the difficultyin handling it and forming it into appropriate semiconductor devices.

Nevertheless, over the last decade much progress has been made in growthtechniques for silicon carbide and are reflected, for example, in U.S.Pat. Nos. 4,912,063; 4,912,064; Re. Pat. No. 34,861; U.S. Pat. Nos.4,981,551; 5,200,022; and 5,459,107; all of which are either assigned,or exclusively licensed, to the assignee of the present invention. Theseand other patents that are commonly assigned with the present inventionhave sparked worldwide interest in growth techniques for silicon carbideand thereafter the production of appropriate semiconductor devices fromsilicon carbide.

One particular growth technique is referred to as "chemical vapordeposition" or "CVD." In this technique, source gases (such as silaneSiH₄ and propane C₃ H₈ for silicon carbide) are introduced into a heatedreaction chamber that also includes a substrate surface upon which thesource gases react to form the epitaxial layer. In order to help controlthe rate of the growth reaction, the source gases are typicallyintroduced with a carrier gas, with the carrier gas forming the largestvolume of the gas flow.

Chemical vapor deposition (CVD) growth processes for silicon carbidehave been refined in terms of temperature profiles, gas velocities, gasconcentrations, chemistry, and pressure. The selection of conditionsused to produce particular epilayers is often a compromise among factorssuch as desired growth rate, reaction temperature, cycle time, gasvolume, equipment cost, doping uniformity, and layer thicknesses.

In particular, and other factors being equal, uniform layer thicknessestend to provide more consistent performance in semiconductor devicesthat are subsequently produced from the epitaxial layers. Alternatively,less uniform layers tend to degrade device performance, or even renderthe layers unsuitable for device manufacture.

In typical CVD processes, however, a phenomenon known as "depletion"occurs and is described as the loss of source gas concentration as thesource and carrier gases pass through the reaction vessel. Moreparticularly, in typical CVD systems, the source and carrier gases flowparallel to the substrate and the epitaxial growth surface. Because thesource gases react to form the epitaxial layers, their concentrationtends to be highest at the gas entry or "upstream" end of the reactorand lowest at the downstream end. In turn, because the concentration ofsource gases decreases during the travel of the source gases through thereactor, epitaxial layers tend to result that are thicker at theupstream end and thinner at the downstream end. As noted above, thislack of uniformity can be disadvantageous in many circumstances, and isparticularly troublesome when thicker epitaxial layers are desired ornecessary for certain devices or device structures.

In growth techniques for other semiconductor materials (such assilicon), the problem can be addressed by fairly straightforwardtechniques such as rotating the substrate (typically a wafer) upon whichthe epitaxial layer is being grown. Such techniques become much morecomplex and difficult, however, when carried out at the much highertemperatures required to grow epitaxial layers of silicon carbide.Typically, the susceptors used for silicon carbide growth processes mustbe formed from highly purified graphite with a high purity coating ofsilicon carbide. When moving parts are formed from such materials, theytend to be rather complex and prone to generate dust because of theabrasive characteristics of the silicon carbide. Thus, such mechanicaland motion-related solutions to the depletion problem are generallyunsatisfactory for silicon carbide because of the mechanicaldifficulties encountered and the impurities that must otherwise becontrolled. Accordingly, a need exists for chemical vapor depositiontechniques for the epitaxial growth of silicon carbide that produce moreuniform epitaxial layers, and yet do so without introducing additionalimpurities or mechanical complexity to the process.

OBJECT AND SUMMARY OF THE INVENTION

Therefore, it is an object of the present invention to provide a methodfor obtaining more uniform epitaxial layers of silicon carbide. Theinvention meets this object with an improved chemical vapor depositionmethod that increases the uniformity of silicon carbide epitaxial layersand that is particularly useful for obtaining thicker epitaxial layers.The method comprises heating a reactor to a temperature at which siliconcarbide source gases will form an epitaxial layer of silicon carbide ona substrate in the reactor; and then directing a flow of source andcarrier gases through the heated reactor to form an epitaxial layer ofsilicon carbide on the substrate with the carrier gases comprising ablend of hydrogen and a second gas in which the second gas has a thermalconductivity that is less than the thermal conductivity of hydrogen sothat the source gases deplete less as they pass through the reactor thanthey would if hydrogen is used as the sole carrier gas. In certainembodiments the second gas is also preferably chemically inert withrespect to the chemical vapor deposition reaction.

In another aspect the invention comprises a silicon carbide epitaxiallayer with a highly uniform thickness as evidenced by its standarddeviation of thickness along its cross section.

The foregoing and other objects and advantages of the invention and themanner in which the same are accomplished will become clearer based onthe following detailed description taken in conjunction with theaccompanying drawings in which:

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of a chemical vapor depositionsystem that is illustrative of those that can be used with the presentinvention;

FIGS. 2 and 3 are plots of wafer thickness versus distance from theupstream edge of epitaxial layers grown using prior art techniques;

FIG. 4 is a plot of wafer thickness versus distance from the upstreamedge of an epitaxial layer grown using the method of the presentinvention;

FIG. 5 is a plot of wafer thicknesses versus distance from the upstreamedge for the respective epitaxial layers grown on three adjacent wafersin a single reactor using the method of the present invention; and

FIG. 6 is a photograph taken with a scanning electron microscope ("SEM")of a cleaved cross-section of a substrate with an epitaxial layer grownaccording to the present invention.

DETAILED DESCRIPTION

The present invention is an improved chemical vapor deposition methodthat increases the uniformity of silicon carbide epitaxial layers andthat is particularly useful for obtaining thicker epitaxial layers. Inits method aspects, the invention comprises heating a reactor to atemperature in which silicon carbide source gases will form an epitaxiallayer of silicon carbide on a substrate in the reactor; and thereafterdirecting a flow of source and carrier gases through the heated reactorto form an epitaxial layer of silicon carbide on the substrate with thecarrier gases comprising a blend of hydrogen and a second gas in whichthe second gas has a thermal conductivity that is less than the thermalconductivity of hydrogen so that the source gases deplete less as theypass through the reactor than they would if hydrogen is used as the solecarrier gas. In certain embodiments, the second gas is preferablychemically inert with respect to the chemical vapor deposition reaction.

In preferred embodiments, the second carrier gas comprises argon. Argonhas a number of advantages with respect to the present invention. Inparticular, argon has a significantly lower thermal conductivity thandoes hydrogen. The presence of argon thus moderates the thermalconductivity of the carrier gas which in turn moderates the rate atwhich the source gases deplete as they move through the reactor.

As another advantage, argon is a "noble" gas meaning that it tends toavoid reacting with other elements or compounds under almost anyconditions. Thus, argon avoids any undesired effect on the epitaxialgrowth substrate, on the epitaxial layer being grown, or on the othergases in the system. It will be understood, however, that the secondcarrier gas is not limited to argon, but can be functionally selected to(1) moderate the thermal conductivity of the carrier gas and (2) avoidundesired reactions with the source gases, the substrate, or theepitaxial layer.

In preferred embodiments, the carrier gases are blended with a greateramount of hydrogen and a lesser amount of the second carrier gas. Inmost preferred embodiments, where the blend is formed of hydrogen andargon, the blend is preferably at least 75% by volume flow of hydrogenand most preferably up to about 90% by volume flow of hydrogen.Additionally, the blend is not necessarily limited to hydrogen and thegas with the lower thermal conductivity. If desired, another gas can bepresent (such as helium) provided that the overall blend meets thefunctional qualifications set forth above.

It will be understood that the volumes as described herein refer to flowvolume on a per minute basis, which is a typical method of measuring theamounts of gases used in chemical vapor deposition systems.

In heating the reactor, the temperature should be high enough for theepitaxial growth of silicon carbide, but lower than the temperature atwhich the hydrogen carrier gas will tend to etch the silicon carbide.Preferably the system temperature is maintained at less than about 1800°C. and most preferably between about 1500° and 1650° C. At temperaturesabove about 1800° C., different types of reactions tend to take place;see e.g., Kordina et al., Growth of SiC by "Hot-Wall" CVD and HTCVD,Phys. Stat. 501(B) 202, 321 (1997).

The invention has been found to be particularly useful when the sourceand carrier gases are directed over a silicon carbide substrate, andmost preferably one selected from the group consisting of the 4H and 6Hpolytypes, and through the reactor in a direction parallel to theepitaxial growth surface.

FIG. 1 is a schematic diagram of a reactor system that is exemplary ofthose useful with the present invention. The basic structure andarrangement of such a chemical vapor deposition system is generally wellknown to those of ordinary skill in this art and can be used by those ofordinary skill in this art to practice the invention without undueexperimentation.

In FIG. 1 the overall CVD system is broadly designated at 10. The systemincludes a reactor chamber 11 which contains a susceptor 12. Thesusceptor 12 is typically heated by an inductive technique (such asradio frequency) using the electrodes 13 on the exterior of the reactor11. A substrate 14 rests on the susceptor 12 so that as the radiationfrom the electrodes 13 heats the susceptor 12, the susceptor heats thesubstrate 13.

The system includes a supply of source gases and carrier gasesschematically diagramed at 15 and 16, respectively. These are directedto the reactor 11 through an appropriate series of passageways or tubesgenerally designated at 17 and flow through the reactor as indicated bythe curved line 20. It will be understood that the line 20 is simply forillustrative and schematic purposes and is not otherwise representativeof the exact flow pattern of gases in a chemical vapor depositionsystem. The gases then exit through a similar set of tubes orpassageways 21 at the downstream end of the reactor 11.

A number of comparative examples demonstrate the advantages of thepresent invention and are summarized in Table 1 and FIGS. 2-5. All ofthe data was collected from experiments conducted at Cree Research, Inc.in Durham, N.C., the assignee of the present invention. As set forththerein, epitaxial layers of silicon carbide were grown on siliconcarbide substrates using either prior techniques (i.e., hydrogen aloneas the carrier gas) or the present invention (a blend of hydrogen andargon as the carrier gas). In each case, the source gases were silaneand propane provided at a significantly smaller flow rate than thecarrier gas.

                  TABLE 1                                                         ______________________________________                                               Average                                                                       thickness                                                                              Standard   standard dev/                                                                          Carrier gas                               Example                                                                              (μm)  deviation (∞m)                                                                     mean (%) (1/min)                                   ______________________________________                                        1      28.5     1.61       5.66     44 H.sub.2                                2      58.7     1.33       2.26     60 H.sub.2                                3      26.0     0.61       2.34     40 H.sub.2 + 4 Ar                         4      28.8     0          0        60 H.sub.2 + 1 Ar                         5      27.5     0          0        60 H.sub.2 + 2 Ar                         6      23.8     0          0        60 H.sub.2 + 4 Ar                         ______________________________________                                    

The samples were measured using a Scanning Electron Microscope (SEM).The wafers were cleaved along the flow direction. They were then placedon the edge in the SEM. Since the layers were much lower doped than thesubstrate, contrast between the layer and the substrate was observed(FIG. 6). The layer thickness could thus be measured. As shown in FIGS.2-5, by measuring the thickness in this way on several equidistantpoints along the cleaved edge, the thickness uniformity could becalculated. There are other techniques for measuring the thicknessuniformity, which are not described herein. Removing the data pointsassociated with the epi-crown (e.g., 2 mm closest to the waferperimeter) is nevertheless common to all techniques in order toreproduce the uniformities shown in Table 1.

The thicknesses of the resulting epitaxial layers were measured atbetween 10 and 15 positions across the diameter of each resulting wafer.The average (i.e., statistical mean) thickness, the standard deviation,and the percentage deviation (standard deviation expressed as apercentage of the average thickness.) were then measured for each wafer.In order to prevent edge effects from mischaracterizing the results fromthe prior art or the invention, either one or two data points wereremoved from the population prior to the calculation. It will beunderstood that these data points were not removed at random toartificially enhance the results. Instead, data points at one or both ofthe wafer edges were removed in order to avoid including the "epi-crown"that is generally commonly found in epitaxial growth and that isgenerally unrelated to the depletion effect.

As FIGS. 2, 3 and 4 demonstrate, the invention provides a dramaticimprovement in the thickness uniformity for epitaxial layers. Forexample, using hydrogen alone as the carrier gas (FIGS. 2 and 3), thepercentage deviation was 5.66% and 2.66% with data points measured onthe epi crown removed. Using the invention, however, a percentagedeviation of 2.34% was obtained for the same hydrogen-alone flow ratethat gave the 5.66% deviation. The beneficial effect of the invention iseven more evident when used with several wafers that are placed onebehind another in the flow direction of the reactor. FIG. 5 illustratesthese results and shows that the uniformity for all three wafers isfavorably comparable with the uniformity of single wafers grown underthe same conditions.

FIG. 2 illustrates the edge thickness variations using a prior arttechnique of hydrogen alone as the carrier gas at a flow rate of 44liters/minute. FIG. 3 illustrates the edge thickness variations using ofhydrogen alone at a flow rate of 60 liters/minute. In contrast, FIGS. 4and 5 illustrate the improved results using the present invention. Inparticular, FIG. 5 illustrates the advantages of the invention when itis used in a multiple-wafer growth system. As FIG. 5 illustrates, thedeviation across three wafers using the method of the invention isfavorably similar to the deviation across one wafer (e.g. FIG. 3) usingthe prior art techniques.

Thus, in another aspect, the invention comprises a silicon carbideepitaxial layer with a standard deviation of thickness along its crosssection of less than 3% when the data points measured on the epi-crownare dropped from the population. In more preferred embodiments, thestandard deviation is less than 2% when the two data points from theepicrown are dropped from the population, and in a most preferredembodiment, the standard deviation is less than 1%.

It will be understood, of course, that the term epitaxial layer impliesthe presence of a substrate, and in preferred embodiments the substrateis a single crystal silicon carbide substrate selected from the groupconsisting of 4H and 6H polytypes of silicon carbide.

As used herein, the terms "mean," "standard deviation," "sample," and"population," are used in their normal sense. These values anddefinitions are well understood within the field of statistics and thustheir definition and manner of calculating them will not otherwise bediscussed in detail.

A blend of hydrogen and argon is preferred over pure argon as a carriergas because pure argon is generally relatively hard to purify, issomewhat expensive, and on an empirically observed basis, it seems toharm material quality, while hydrogen seems to purify the growingmaterial. Stated differently, hydrogen as a carrier gas appears to havesome scavenging properties. Because of its low thermal conductivity, acarrier gas of pure argon would also tend to retard growth rates beyonda point that is generally desirable.

The selected proportion of the mix of argon and hydrogen can depend on anumber of factors. These factors are, however, relatively well known inthe art, and thus once the concept of the invention is understood, theblend can be selected by those of ordinary skill in the art withoutundue experimentation. As examples (rather than limitations), however,the amount of argon blended with the hydrogen will depend on items suchas the length of the hot zone, the cost of argon, total gas flow, gaspurity, and zone temperature. In particular, in most cases, the longer(in distance) the hot zone extends and the higher the expected orrequired temperature, the more argon is desirably used to moderate thedepletion effects.

Additionally, the price of argon (as noted above, it is expensive) is apractical, although not theoretical, limitation on how much argon ismost desirably used.

A third factor is total gas flow. A lower total gas flow is generallyadvantageous in a CVD system because it moderates the load on thepumping system, requires less energy and reduces turbulence, and avoidscooling the susceptor.

The purity of argon represents another factor. Because argon cannot bepurified as well as hydrogen, the amount used is preferably minimized tocorrespondingly minimize any associated impurities. Fortunately, becauseargon's thermal conductivity is approximately one-tenth that ofhydrogen's, a relatively small fraction of argon is sufficient to carryout the present invention.

All of the problems associated with uniform thickness control duringchemical vapor deposition are exacerbated when thicker layers are beinggrown. Thus, the invention provides an even more noticeable improvementfor growing thicker layers. Furthermore, because the invention merelyrequires blending gases, it avoids the moving parts and mechanicalcomplexity of some other systems for reducing depletion.

In the drawings and specification, there have been disclosed typicalembodiments of the invention, and, although specific terms have beenemployed, they have been used in a generic and descriptive sense onlyand not for purposes of limitation, the scope of the invention being setforth in the following claims.

That which is claimed is:
 1. A method of forming epitaxial layers ofsilicon carbide on an appropriate substrate by chemical vapordeposition, the method comprising:blending silicon carbide source gasesare with a first carrier gas; directing the source gases into a reactorthat contains a substrate over which the carrier and source gases flowover the substrates in an upstream to downstream orientation parallel tothe epitaxial growth surface of the substrate; heating the reactor to atemperature at which the source gases will react to form an epitaxiallayer of silicon carbide on the substrates in the reactor; and whileblending a second carrier gas with the first carrier gas, and in whichthe second carrier gas has a thermal conductivity that is less than thethermal conductivity of the first carrier gas, and wherein the secondcarrier gas is present in an amount that moderates the temperaturesufficiently to reduce or eliminate source gas depletion during thegrowth of an epitaxial layers of silicon carbide on the substrate, butless than an amount that would reduce the temperature sufficiently toprevent the source gases from reacting to form the epitaxial layer.
 2. Achemical vapor deposition method according to claim 1 wherein the secondgas is chemically inert with respect to the chemical vapor depositionreaction.
 3. A chemical vapor deposition method according to claim 1wherein the second carrier gas comprises argon.
 4. A chemical vapordeposition method according to claim 1 wherein the first carrier gas isselected from the group consisting of helium and blends of helium andhydrogen.
 5. A chemical vapor deposition method according to claim 1wherein the step of blending the carrier gases comprises blending agreater amount of hydrogen with a lesser amount of the second carriergas.
 6. A chemical vapor deposition method according to claim 1 whereinthe source gases comprise a silicon-containing compound and acarbon-containing compound.
 7. A chemical vapor deposition methodaccording to claim 6 wherein the source gases comprise silane andpropane.
 8. A chemical vapor deposition method according to claim 7comprising heating the system to a temperature less than about 1800° C.9. A chemical vapor deposition method according to claim 7 comprisingheating the system to a temperature of between about 1500° and 1650° C.10. A chemical vapor deposition method according to claim 1 comprisingdirecting the gas flow through the reactor in a direction parallel tothe epitaxial growth surface.
 11. A chemical vapor deposition methodaccording to claim 1 comprising directing the source and carrier gasesover a silicon carbide substrate selected from the group consisting ofthe 4H and 6H polytypes.
 12. A chemical vapor deposition methodaccording to claim 1 wherein the second carrier gas is chemically inertwith respect to the chemical vapor deposition reaction and the siliconcarbide.
 13. In a method of forming epitaxial layers of silicon carbideon appropriate substrates by chemical vapor deposition, and in whichsilane and propane source gases are blended with hydrogen as the carriergas and directed into a reactor that is heated to a temperature ofbetween about 1500 and 1650° C. at which the silane and propane willreact to form an epitaxial layer of silicon carbide on a substrate, theimprovement comprising:blending argon with the hydrogen carrier gas, andwherein the argon is present in an amount that moderates the temperaturesufficiently to reduce or eliminate source gas depletion during cvdgrowth, but less than an amount that keeps the source gases fromreacting to form the epitaxial layer.
 14. A chemical vapor depositionmethod according to claim 13 wherein the blend of hydrogen and argoncomprises more than 75 percent by volume flow of hydrogen.
 15. Achemical vapor deposition method according to claim 14 wherein the blendcomprises about 90 percent by volume flow of hydrogen.
 16. A chemicalvapor deposition method according to claim 13 comprising directing thegas flow through the reactor in a direction parallel to the epitaxialgrowth surface.
 17. A chemical vapor deposition method according toclaim 13 comprising directing the source and carrier gases over asilicon carbide substrate selected from the group consisting of the 4Hand 6H polytypes.
 18. In a method of forming epitaxial layers of siliconcarbide on a plurality of appropriate substrates by chemical vapordeposition by:blending silicon carbide source gases are with a firstcarrier gas; directing the source gases into a reactor that contains aplurality of substrates linearly arranged along the gas flow path in thereactor so that the carrier and source gases flow over the substrates inan upstream to downstream orientation parallel to the epitaxial growthsurface; and heating the reactor to a temperature at which the sourcegases will react to form an epitaxial layer of silicon carbide on thesubstrates in the reactor; the improvement that comprises: blending asecond carrier gas with the first carrier gas, and in which the secondcarrier gas has a thermal conductivity that is less than the thermalconductivity of the first carrier gas, and wherein the second carriergas is present in an amount that moderates the temperature sufficientlyto reduce or eliminate source gas depletion during the growth ofepitaxial layers of silicon carbide on the substrates, but less than anamount that would reduce the temperature sufficiently to prevent thesource gases from reacting to form the epitaxial layer.
 19. A chemicalvapor deposition method according to claim 18 wherein the second carriergas is chemically inert with respect to the chemical vapor depositionreaction and the silicon carbide.
 20. A chemical vapor deposition methodaccording to claim 18 wherein the first carrier gas comprises hydrogenand the second carrier gas comprises argon.
 21. A chemical vapordeposition method according to claim 18 wherein the step of blending thecarrier gases comprises blending a greater amount of the first carriergas with a lesser amount of the second carrier gas.
 22. A chemical vapordeposition method according to claim 18 wherein the source gasescomprise a silicon-containing compound and a carbon-containing compound.23. A chemical vapor deposition method according to claim 22 whereinsource gases comprise silane and propane.
 24. A chemical vapordeposition method according to claim 23 comprising heating the system toa temperature less than about 1800° C.
 25. A chemical vapor depositionmethod according to claim 23 wherein the reactor is heated to atemperature of between about 1500° and 1650° C.
 26. A chemical vapordeposition method according to claim 18 comprising directing the gasflow through the reactor in a direction parallel to the epitaxial growthsurface.
 27. A chemical vapor deposition method according to claim 18comprising directing the source and carrier gases over a silicon carbidesubstrate selected from the group consisting of the 4H and 6H polytypes.